Combinations of vinyl aqueous emulsions and resinous acetone-formaldehyde reaction products



United States Patent 2,859,192 7 COMBINATIONS on vnwr AQUEOUS EMUL-SIONS AND RESINOUS ACETONE-FORMALDE- HYDE REACTION PRODUCTS Mortimer T.Harvey, South Orange, and Peter L. Rosamilia, Newark, N. .L', assignorsto Harvel Research forporation, ,Irvington, N. J., a corporation of Newersey' No Drawing. Application september 22, 1955 Serial No. 536,037

8 Claims. ct zen-29.6

means of spreader rolls, for example, to paper or the like which may ormay not have its surface coated with some other. material such asvarnish, resin, dextrine, glue, etc. After being coated with saidemulsion from the spreader rolls, the paper carrying the emulsion has alayer of newsboard, for example, applied thereto to provide a multipleelement laminated structure of paper and newsboard with the emulsionadhesive therebetween securing said layers to 'eachother. Such laminatedstructures find a variety of applications; among which is that of bottlecap liners after being' sheared into appropriate shape and size,generally in discform.

' For a considerable time, it has been known to the art that saidemulsions have a number of inherent disadvantages. Among some of themare the following: (a) when spreading rolls are employed for coating theaqueous cm'ulsions, considerable foaming builds .up on the rolls whichdeleteriously afiects the bond of the finished product; (b) when thecommon defoamers'are vusedrto prevent the building up of foam on thespreading rolls, the

strength of the bond of the finished product is considerably decreased;(c), when certain types of paper, such'as the varnish or resin coatedtype papers'have a coating of said emulsion applied thereto and bondedto newsboard or thelike, the finished product develops a concavecurling. This is disadvantageous especially" when that finished productis cut into discs for use as bottle cap liners.

It has been foundthat the fingers of machines which 2,859,192 Patentedov. 19 5 8 ice for sixteen hours in the presence of lime measuring 5% ofits weight, to be converted to the dry and substantially infusiblestate. 'The mole ratio of acetone to formaldehyde in the reaction may belet acetone to 2-6 of formaldehyde-and preferably -1 of acetone to 2-5offormale dehyde. The. amount of said acetone-formaldehyde reactionproduct combined with said aqueous emulsion is such that for each 4parts of the former there is 1-16 parts of the vinyl resin in thelatter. The acetone-formaldehyde reactionproducts are water soluble and.of such viscosity that when 4 parts thereof are dissolved in 1 part ofwater, the resultant solution shall have viscosity at 25 C. ofat least600 centipoises and for adhesive purposes, LOGO-10,000 centipoises.

By providing said novel combinations, we have found them to have thefollowing advantages as laminating media over said aqueous emulsions inthe absence of the acetone-formaldehyde reaction products and some ofthem are as follows; (a) the presence of 'the acetoneformaldehydereaction products in the combination reduced'and sometimes completelyeliminated foaming at the spreader rolls without in anyway decreasingthe. tensile strength of the bond; (b), the presence of the.acetone-formaldehyde reaction products reduces the tendency of thelaminated struc'ture'to curl or buckle thus a more nearly flat finishedproduct is obtainable; (c),

tively reduces the liability of delamination;-and (d) sun another factorof importance is that a less expensive and J reaction products.

handle such linings have difficulty holding a very concave fining andconsequently it drops ofi the fingers, thus disrupting continuousvoperation, (d) after several months of storage of saidfinished productthere is a decrease in the tensile strength of the bond and sometimesdelamination of the layers due to the excessive drying out of theadhesive. 7

After extended experimentation, has been discovered that said emulsionsmay be modified to provide novel compositions of exceptional propertiesand also to provide novel products therewith; We have foundthat combining resinous reaction products of acetone and formaldehyde with saidaqueous emulsions resulted in combinations which were far superiorinmany respects to the aqueous emulsions without said' additionllTheresinous reaction products of a'cetone andformaldehyde are pro-- ducedby reacting acetone and formaldehyde under alkaline, conditions, Saidacetone-formaldehyde r reaction productsmay be eharacterized asbeingwater-soluble and;

shat insati b e, psm b kinsat 300? F;

' 140 C., gels at roomtemperature within 4 hourslupon better product isavailable because of the lower costo said acetone-formaldehyde reactionproducts.

The following is given merely by way of illustrating a method forproducing acetone-formaldehyde resinous Example)! 7 300 lbs. of acetonetogether with 1700 lbs. of formaldehyde (37% concentration inwater) werecharged into, an autoclave unit with the steam on and the' stirringequipment-jin operation to raise the temperature. of the mix toapproximately F. In a separate container there was made up an aqueoussolution of caustic soda consisting of 25 lbs. NaOH and 60 lbs. water.This solution was divided into 4 equal portions. The first portion ofcaustic soda solutionwas added and the steam; cut ofi. The temperatureof the mixrises to F. and the cold water is turned on as an exothermicreaction takes place and the temperature slowly rises to 200 F. thenslowly begins to fall; the second portion of caustic soda-water solutionis added whereupon the temperature again rises to 200 F. Upon cooling to185 F. the pro cedure is repeated allowing the temperature to rise andfall between the additions of caustic soda-water solution and keepingthe 'cold water on the jacket at all times. The mass is then allowed tocool to F. at which time the cold water is shut 0E. Vacuum is turned onV keeping the vent of the autoclave open. The vent is: slo'wly'closedand the steam turned on. Dehydration may be continued to produce a resinof 75%-'-100% solids! The amount of resin produced measured more than75% of the combined weights of the acetone and formalde hydein theoriginal charge. The resin isamber colored is thermosetting. and; isstable for atleast 6 months at 30 C., cures to the .infusiblestatein"two hours at adding 10% lime a'nd'an 80% aqueous solution thereof at 25C. has. a viscosity ofjabout" 800 "centipois'es anda is hereinafterknown as: product A? In the dehydration 'step, it

' isipreferred that it" I terminated when theape'rcentagelsolids"is-between 7 5%--'- tion is the acetone-formaldehyde reaction product.Then said reaction product may be treated to increase itsviseosity,..:and; tozzdecrease. ;the'. freeiformaldehydescontentiithereof. :Eor-ithat; purpose said saqueousErsolution ofusaidspartiallys dehydrated acetoneeformaldehydei' areac-vtionz'productl is: placerhrin ;a reacting atesselrandl there-sisaddedzthereto-zin ,aqueous solution :ofran-alkali: andpprbf:erablygaemildzalkalirrsuclr; as: sodium.:sulphite, sodium acetate,:ipotassimnesulphite. :or equivalent :..compourid; :to increaseihfilpHiiOfLthflIIIliX. ;:Ihe heatedislowly to;.-a'stemperatureaof about2509i .Fssandns maintained until thezxiscositymf 24; .partsn'ofithe'.:resin tthereinnrwhen dissolved zin. impart .ofxwater, measuresainoreithanc600 and no: :greaten; than 110,000.; centip oisesyats 25 .C.and when iitaislto be used asramadhesivenmeasures' 2,000- 10,000centipoises at 25 C. This providesla ssirnple, easily;controllableimeth'odzwhichs is teininently :suitable: infactorylpractice'ifonlthickening. or increasing the viscosity of theacetone-formaldehyde tresin' toitheadesiredidegree, and practicallyeliminating :the dangertof =the .resin fioing tofltheiginflisible state.More specifically; for example,- 2'50 slbs. .ofr.- an=280% solution ofsaid f-acetonerformaldehyde .resin, after. the: partial dehydrationstep; is now mixediwith an aqueous solution-consisting ofi approximately7 =-l bs;-of :sodium sulphite dissolv ed in a small amount:-of"-}water;'Fhesmixture i's zheat ed to: approximately 250311 and maintained atthat temperature until a sample of fl parts of' the acetone-formaldehyderesin,

\Whileiin :theaforesaid general examplethereghas described. the rr1ethod;for producing said iresinous rea'c-s' tion productsawith a gratio, ofacetone to formaldehyde being 1 ,4 ,.it;;is understood of course thatthe samerm'et-he od.may"be employed andratio of acetonejandefonnaldehyde-may be; varied .within the limits ;hereinbeforel:set forth, -,to;-produc e-a variety of reaction-products .all ;:of

whieh,--tof ,course,zare water soluble and .thermosetting andservmascomponentsofthisinventiona continuous phase. The 1 percentage .of :said,vinyh:resin' inathenemulsion rmay vary over a comparatiilelyl'wide range-.and. 'may,be. between about 30.%-:5.0% :by weight. To. such-emulsions.:there may'xbexv added= zsaidsr'esinou's acetone-formaldehyde. reactionproducts, ieitheri Ihe. anhydrous form; on in. aqueous .1S0ll1fi0l1,i:depending; upon thefizglesire'd rffsolidsr:content,:- the desiredftronsistency, and the, desired: ChiiIaCteIlStiCQDfi :theifinishediprodnct;

In; any;.case, it a ispreferahle that the iquantityunfi there/atersoluble,v .therinosetting acetone-formaldehyde .resinous;product addedis suchrthatforxeach s4 ammereaf added,- ithere; isvpresent =1-l6-sparts.of'zthe lt'zinyl resin 3.:in

therraqueonsrzemul'sion. i Then 'tliis'zniixture;t' zby; a sirn.iszagitated ple agitation, by means fofi amordinary stirrer", W for ashort iperiddspfaitirnerto rend'en' it 'sirbstant iallyhomogeneonssthroughout; lIha-finisheii zproduct ists'till aqueousemulsion which is stable andgin which the aqueous phase has dissolvedtherein the acetone-form aldehyde resin. The finished product is nowcoated on:

said paper by spreader rolls with out foam building upon said rolls andto said coated paper may be applied the newsb oard, for' example, toprovide a..laminated 'strucr ture, of paper and .newsboard with saidfinishediproduct as the adhesive therebetweenand.havingnthe improvedcharacteristics before set forth. This laminated. struc-' ture'may becut to provide improvedlbottle.capliliriers, for example. i

The following are examples of some of the noveherm given by weight ginto said vessel,625,-partsof--anaqueous-solution' ofacetone-formaldehyde reaction "produet-=madeaccording to Example A audconsisting of -parts of wateram 500 partsof the acetone-formaldehydereaction product with the "viscosity of said solution at 25 Ct'being'2236.0

centipoises, and hereinbefore identified product TA After the additionof the-acetone fonnaldehyde solution V the mixture was stirred for about3 O minutes wherebyra substantially uniform -and *st'able :product*hereinafter knowngasproduct Iwas=obtained.

:Examplell 1000 parts of an aqueous emulsion of'a'vinyl resinwas Vplaced into a glass vessel. "Thevinyl resin wasprese'nt i in amountequal to 50% bywei'ght of the emu a. n and was solid polyvinyl chloride(Vinylite QYHA according to Example'A, consisting essentialllyjcif 50ofwater and 200* parts .of acetone=formaldehyde reaction: -pr0duct, said'solution'havinga viscosity at 25 oarmm centipoisesand'hereinbeforeiidentified as prodiicl" The 'mix' was.rapi'dlystirred'jfor about '20 minutessto .r vide a stable; homogeneousproduct hereinaftefikn as'productfII.

a ,rExampleiIII l000-part's-ofanaqueous'emulsion ofa placed'ina-glassvessel. "Thevinylresinwas present 7 amount equal to 49%.'by'weight "ofthexemulsion .andzwas" solid polyvinyl acetate (fVinyliteAYABZ). pT'henthere was addedthereto 500 parts 'of an .aqueons 'solutionof acetone-formaldehyde reactionproduct made according to Example A andconsisting essentially ofglOQ; parts of water and ;400 1 parts ofacetonefornialdehyde. reaction product, the'viscosity ofisa'id solutionat 25 fCJbeingSOQQ;

.centipoises and. hereinbefore identified as produbtfBfA;

The mix'was' stirred for 20 minutes torprovide .ajstable homogeneousproduct hereinafter 'known; asjproduet Examples V VI 2' "Employingsthesame.- procedure,-.components and pro; portion ofparts .except thatproducLAjs.silhstituteiiior: 7 products lA-BA of'Examplesl-JIIrespectively,

.IV, V'aHf 1lVI were prepared;

WhilejtheJnovel combinations of this. ipventi n,e1 r-' amples of whichare products .I-VI and; especially produets I HITfi11d application asadhesives for a'varietyof laini-l, nated structures/which, besidesnewsboard'and pa r" which weregivenmerelyby way'oi'examplwmayinclutk vcloth, wood, etc 'theyand"especially productslV vI nrayl alsoemployed-as coating media from which the wa ter. may-be dissipatedwith=or=without heating For ezzafiilfl r they may beaapplied toavbasezand 1 st. there was chargedinto'thevessel, 250 parts ofan'aqueous solution of acetone-formaldehyde.reaction produqf m3 V ucts.

2,ss9,19a

drive off the water, or may be used as adhesives in the manufacture ofwooden furniture, laminated wood, etc.

Example 1 Using a reverse roller type coater, one face of a 70 1b. kraftpaper is one-side coated with products IV-VI respectively. The amount ofsuch coating may vary and in general may be approximately 1 lb. of suchcoating per about yards of the paper coated. Then the so coated paper ispassed through an oven maintained at 300 F. whereby the water is drivenoff to provide a dry coated paper, with the coating having excellentadhesion.

Example 2 Product I, II or H1 is spread in a thin film on an 80 lb.kraftpaper, by the use of a roller and smoothed with a Mayer bar andusing about 1 lb. of such product for 10 square yards of paper. Thenwhile still wet, newsboard is laid over said coated surface and'the wetlamination is wound to form a roll. The roll is allowed to remain atroom temperature for 48 hours after which time is may be unwound, and itwill be found to be a strong lamination with the original coatingmaterial being in the substantially dry state. If desired, the exposedfaces of either or both the newsboard or kraft paper may be subsequentlycoated with wax or other coating medium.

Since certain changes may be made in the above compositions of matterand difierent embodiments of the invention could be made withoutdeparting from its scope, it is intended that all matter contained inthe above description shall be interpreted asillustrative and not in alimiting sense.

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed and all statements of the scope of the invention, which as amatter of language might be said to fall therebetween, and that they areintended to be inclusive in scope and not exclusive, in that, ifdesired, other materials may be added to my novel composition of matterherein claimed without departing from the spirit of the invention.Particularly it is to be understood that in said claims, ingredients orcomponents recited in the singular are intended to include compatiblemixtures of said ingredients wherever the sense permits.

This application is a continuation-in-part of our copending applicationSerial No. 252,411, filed October 20, 1951, now abandoned. a

Having thus described our invention, we claim:

1. A novel composition of matter comprising (a) an aqueous emulsion of anormally solid vinyl resin selected from the group consisting ofpolyvinyl acetate, polyvinyl chloride and copolymers of vinyl chlorideand vinyl acetate and (b) resinous reaction product of acetone andformaldehyde produced under alkaline conditions, said resinous reactionproduct being water soluble and thermosetting, the ratio by weight ofsaid vinyl resin to said resinous reaction product being 4 parts of saidresinous reaction product to 1-16 parts of said vinyl resin, the

that an aqueous solution thereof measuring 4 parts by weight of saidresinous reaction product to 1 part by weight of water is in the rangeof 600 to 10,000 centipoises at 25 C. said (b) being dissolved in theaqueous phase of (a) 2. A novel composition of matter defined in claim1, but with the viscosity of such aqueous solution being in the range of2,000 to 10,000 centipoises at 25 C.

3. A novel composition of matter comprising an aqueous emulsion ofnormally solid polyvinyl acetate and a resinous reaction product ofacetone and formaldehyde produced under alkaline conditions and beingwater soluble and thermosetting, the ratio by weight of said polymer tosaid resinous reaction product being 4 parts of the latter to 1-16 partsof the former, the viscosity of said resinous reaction product beingsuch that an aqueous solution thereof measuring 4 parts by weight ofsaid resinous reaction product to 1 part by weight of water is in therange of 600 to 10,000 centipoises at 25 C. said resinous reactionproduct being dissolved in the aqueous phase of said emulsion.

4. A novel composition of matter defined in claim 3, but with theviscosity of such aqueous solution being in the range of 2,000 to 10,000centipoises at 25 C.

'5. A novel composition of matter comprising an aqueous emulsion ofnormally solid polyvinylchloride and a resinous reaction product ofacetone and formaldehyde produced under alkaline conditions and beingwater soluble and thermosetting, the ratio by weight of said polymer tosaid resinous reaction product being 4 parts of the latter to 1-l6 ofthe former, the viscosity of said resinous reaction product being suchthat an aqueous solution thereof measuring 4 parts by weight of saidresinous reactionproduct to 1 part by weight of water is in the range of600 to 10,000 centipoises at 25 C. said resinous.

reaction product being dissolved in the aqueous phase of said emulsion.r

6. A novel composition of matter defined in claim 5, but with theviscosity of such aqueous solution being in the range of 2,000 to 10,000centipoises at 25 C.

7. A novel composition of matter comprising an aqueous emulsion of anormally solid copolymer of vinyl acetate and vinyl chloride and aresinous reaction product of acetone and formaldehyde produced underalkaline conditions and being water soluble and thermosetting, the ratioby weight of said resinous reaction product to said copolymer being 4parts of the former to 1 16 parts of the latter, the visosity of saidresinous reaction product being such that an aqueous solution thereofmeasuring 4 parts by weight of said resinous reaction product to 1 partby weight of water is in the range of 600 to 10,000

centipoises at 25 C. said resinous reaction product being.

dissolved in the aqueous phase of said emulsion.

8. A novel composition of matter defined in claim 7, but with theviscosity of such aqueous solution being in the range of 2,000'to 10,000centipoises at 25 C.

References Cited in the file of this patent UNITED STATES PATENTS1,514,508 Ellis NOV. 4, 1924

1. A NOVEL COMPOSITION OF MATTER COMPRISING (A) AN AQUEOUS EMULSION OF ANORMALLY SOLID VINYL RESIN SELECTED FROM THE GROUP CONSISTING OFPOLYVINYL ACETATE, POLYVINYL CHLORIDE AND COPOLYMERS OF VINYL CHLORIDEAND VINYL ACETATE AND (B) RESINOUS REACTION PRODUCT OF ACETONE ANDFORMALDEHYDE PRODUCED UNDER ALKALINE CONDITIONS, SAID RESINOUS REACTIONPRODUCT BEING WATER SOLUBLE AND THERMOSETTING, THE RATIO BY WEIGHT OFSAID VINYL RESIN TO SAID RESINOUS REACTION PRODUCT BEING 4 PARTS OF SAIDRESINOUS REACTION PRODUCT 1-16 PARTS OF SAID VINYL RESIN, THE VISCOSITYOF SAID RESINOUS REACTION PRODUCT BEING SUCH THAT AN AQUEOUS SOLUTIONTHEREOF MEASURING 4 PARTS BY WEIGHT OF SAID RESINOUS PRODUCT TO 1 PARTBY WEIGHT OF WATER IS IN THE RANGE OF 600 TO 10,000 CENTIPOISES AT 25*C.SAID (B) BEING DISSOLVED IN THE AQUEOUS PHASE OF (A).